Method of electrolytically producing aluminum



- and appliances Patented Dec. 22, i925 i J'enu} nLnAILsBAcK, orsHnEvEPoRT, LOUISIANA.

l Mamet; I ecweoimfmr y rnonticinc YALUMINUM.

wNo Drawing.

a citizen of the UnitedfStates, residing at Shreveport, "in tlie parish of Caddo and State of Louisiana,have invented'ce'r'tain 7 new and useful? "Improvements in 'Methods of which thefollovvi'ng 'is specification.

This invention to certain new, and, useful improvements" in methods of electro lyticallyseparating or producing aluminum, At present aluminum is. extensively pro duced by the Hall the. Heroult processes, in Which processes alumina is fused salts and separated the electricfcurrent into metallic aluminum and oxygen as" it was an electrolyte.

The vari' us forms electric furnaces utilized for the "production of aluminum, 'magnesium, calcium, etc,, are adaptable to my process, th e'fmostfinaterial modification being the, addition r meaps to rec'ov'erj the valuable by-product. :1

My improvement 1s concerned with. the chemical problems involved and not the mechanical "problems, the details l of which have been welll'vvorked out. TI ,pro+

pose tomodify'thefchemical procedures of a, .the electrolytic "process While" continuing lto; 4 utilize the present mechanical procedures l'.

during t which fseparati is used, valuable by o er T em n I if t res us ally" i b rrent "c a i is m f 1 fluo ne which m ixture is" as hefletr c in r -11 t The @Qsenu a xtiirefro'rn which; m n m' o b elect yr c l y p rat d,

,6 .Qf f S d 33 a}? solvent for alumina ons'ists of various pom-,3 binations of; thea fluoride's,andchlorides of minu sodi lcium, tfiicdi m;mv I potassium always bjeing pr esent, the Imolten lqr e andxy n Application filedibctelier. 1,9214- ILSerIiYIINQ' 7.44327;

be subjectd. totheaction of the electric currentby'lniethods already Widely used, to-

gether vvith a method of compounding the improvedlmixture.

The use of the anhydrous chloride or sul- V I p .fide ofaluminum in place of alumina has of Electrolytically ProducingAluminum;been'suggested so as to liberate the metal at alovvergvoltage and save electricv power.

a is ,greater than the cost of the electric power a jthereby rendered unnecessary. or dissolved in amolten mix ture of haloid In any'possible process for the electrolytic productlon of aluminum, every compound "entering into the molten mixture from which it is ltor beseparated, must be anhydrous,- andj" most anhydrous compounds of aluminum are difficult and expensive to prepare.

Inirny'pro'cess, I use the oxide, the cheapest possible;anhydrous compound. 'Yet, I liberatej simultaneouslywith the metallic aluminum,'some element of less affinity for aluminum. than oxygen. 1 This I achieve by modifying? the omposition of the" molten omixturejwhich is subjected to theelectric current.

.Ina fluidfmixture containing various ions usuallythe first pair to be separated by the electricj-current at-the lowest voltage is that otherbyasmaller aflinity than any other .pair;ftherefore, in a molten mixture such as above described,-.-containing ions of aluminui'n sodium, calcium, fluorine, chlorine, and when 1 process ucts Zinay be} re. a

' d "L the voltage required to separate aluminum vand,ox ygen being 2.8;; that required to separate aluminumv and chlorine being 2.0, but

oxygen, the; first pair I would expect to be separated ,vvould: be, ;aluminum and chlorine;

the. separation. of;;;aluminum and chlorine fromg-such a 1n1;xture ;.would leave sodium ox- ]id'e in solutiomnnd the afiinity of aluminum or oxygen being'ggreater than that ofsodium, ,sodium. oxidej would be reduced by odium The, presence oi -sodium or potas- L any negative subforfalum'mum than p. H I h v a "oppositely;charged pair attracted to each Y My '1 pl 'ovement is concerned with thehejlibe tedi ialuminumyalso the liberated hlorin would; ,react upon the oxide of .6

' illiculty caused by' the presence of oxides are diificultly fusible at these tempersodium, I overcome by the elimination of sodium, replacing it with some of the metals, whose oxides are not reducible by aluminum, -namely, lithium, beryllium, magnesium, calcium, strontium, and barium, which met: als hold the oxygen in combination while aluminum is electrolytically liberated at one electrode and some element of less aflin'ity for it than oxygen at the other.'

I further modify the" composition of the molten mixture by introducing therein 10ns of substances of lower aflinity' for aluminum than oxygen, namely, chlorine, bromine, iodine, sulfur, selenium, or tellurium, aluminum being separated from these at lower voltages than from oxygen, thereby realizing the saving ot'electric power sought by the proponents of the use of anhydrous chloride and sulfide of aluminum.

The molten mixture from which I electrolytically separate aluminum is compounded from aluminum oxide and the haloids, sulfides, selenides, and tellurides of aluminum and of thosemetals whose oxides are not reduced by aluminum. The chemical and physical facts involved in compounding the molten mixture from which aluminum is electrolyticall separated are that at the temperatures use the haloids of aluminum and of the metals electro-positive to it are fusible and miscible with each other, while their atures, but are soluble to a limited extent in the fluid haloid mixture.

Many changes in the composition of the molten bath have been proposed in order to modify in a desirable way its density,

fusion point, cost, and solvent .powers forv alumina, but never with the idea of changing the electro-negat'ive element vto be liberated simultaneously with aluminum; orof eliminating by precipitation undesirable compounds which may be incidentally introduced or formed.

Any desirable modifications of its density,

' fusion point, cost or solvent power for alumina achieved by m method, are merely inpotassium'for the purpose of achieving some of the above desirable results is described and claimed in the United States patent to Hall, No. 400,664. In the present process, I substitute entirely lithium for potassium, in-

' cidentally achieving some of the-above dewith aluminum.

"'at various current densities, and-could be recovered if necessary from baths of "reater specific gravity than the metal, as is one in amount of four times a chemical equivalent of the aluminum. v

I have compounded my baths according to published formulas, merely substituting for potassium and sodium, some other metal more electro-positivo than. aluminum. For instance, I have used a bath composed ot seven parts Li AlF and one part of CaF into which I fed a mixture of alumina and .either the sulfide or chloride of lithium, the

bath in the above, instance being lighter than aluminum and fusing below 800.

Hall describes his process as dissolving, alumina in a molten bath of fluorides of. aluminum and of a metal ormetals more e-lectro-positive than aluminum, and then passing the electric current through the fused mass. His conception and that gen erally held since being that the molten bath acts as an inert solvent, not participating in the reaction.

In order to emphasize a broader conception, I discard his term molten bath and use in its place the expression molten mixture, not pretending to distinguish between solvent and solute.

This broader conception will make many details clear. For instance, if into a suitable molten haloid mixture saturated with calcium oxide, I simultaneously introduce aluminum oxide and calcium sulfide, calcium oxide is bound to be precipitated, in which instance by the simultaneous introduction of alumina and calcium sulfide, I actually introduce aluminum sulfide without changing the nature of the so-called molten bath. In like manner, aluminum and magnesium chloride can be simultaneously introduced into a molten bath saturated with magnesia and in effect introduce aluminumchloride into vthe mixture without changing the nature of the molten bath.

To introduce into the molten mixture negative ions of less affinity for aluminum than oxygen while in combination with aluminum, entails the expensive preparation of their anhydrous aluminum compounds, which expensive auxiliary process I avoid by introducing them while they, are combined with some of the metals whose oxides are not reducible byaluminum". This has not been heretofore proposed, 'andis one of the principles I desire to protect.

To realize the advantage of my method in compounding the molten mixture, consider the simultaneous introduction of the ions of "aflinity for it than oxygen.

aluminum and sulfur. .To introduce them in combination as aluminum sulfide entails the expensive preparation of the anhydrous compound, but the simultaneous introduction of.

aluminum oxide into the same mix with the sulfide of lithium or calcium achieves the same result at a fraction of the cost and is a. preferred embodiment of my process.

Another preferred procedure'is to introduce alumina into a fused mixture containing magnesium, beryllium or lithium chloride and electrolyze. i

The advantages arising from the use of the sulfur ion are due to its extreme cheapness and entire lack of poisonous properties. Additional economy of electric power is to be realized by the use of ions of selenium and tellurium.

In addition to its cheapness, an advantage to be derived from the use of the chlorine ion is that at comparatively low temperatures, electrolytically liberated chlorine reacts with the carbon anode, therefore, in addition to their cheapness'the use of chlorides to supply the ion to be simultaneously liberated with aluminum, makes possible the manufacture ofcarbon tetrachloride asja by-product, four pounds of the chloride to one of the aluminum, which at present relative prices is about as valuable as the main product. Like-' may be produced as a ion at so low a temperature that the anode.

will not be consumed at all.

To summarlze, my process consists:

1st. Of the elimination of sodium and potassium from'the molten mixture from which aluminum is to be electrolytically separated because if combined oxygen be a constituent the presence of sodium or potassium renders impossible the simultaneous separation of aluminum and any negative element of les 2nd. Of the substitution of those metals whose oxides-are not reducible by aluminum :for sodium or potassium, because of their ability to hold oxygen in combination, while some element for which aluminum has a less afiinity is liberated at the anode.

3rd. Of the introduction into themolten mixture of ions of elements for which. aluminum .has a less affinity than for oxygen,

which\ elements if sodium or potassium beabsent\ are liberated simultaneously with vention duci 2.'Thel herein described mixture for use in electrolytically separating aluminum comments whose I aluminum by the electric current While com bined oxygen remains in solutio n.

4th. Of the introductlon of 1011s of lower aiiinity for aluminum than the ion of oxygen into the molten mixture containing alumina.

while in combination with some metal other than aluminum with which they form cheaply prepared anhydrous compounds.

5th. Of so constituting the molten bath that upon the simultaneous introduction of two compounds, which contain two ions which it is desired to electrolytically separate these two ions will remain in solution while the other two will precipitate or crystallize out, leaving the molten bath of the same composition as the beginning.

The process above summarized enables us to electrolytically separate aluminum with great saving of electric power, yet Without additional costly chemical processes, to

greatly out the consumption of anode carbon, to; produce by-products of value, and

to eliminate the present loss of cryolite, which will notbe decomposed at those voltages suflicient to decompose the chloride or sulfide of aluminum.

Of the above summarized essentials of my improvement, the useof other negative ions than those of. oxygen such as sulfur, has been suggested but no practical method-0f accomplishing it proposed. No other idea involved'in my improvement has even been 'sug ested.

T e elimination of sodium and potassium is not to bev treated as a negative proposal because the discovery that they are the trouble makers in all existing processes,

while entirely noyel and new, is also the fundamental discovery out of which my inrew, and the ositive act of eliminating t e trouble-ma er is the basic improvementwhich makes all the rest possible.

I claim;

bath for use in the production of aluminum comprising compounds of aluminumgland' a metal whose oxide is not ree by aluminum;

prising a mixture of compounds 'of aluminum and another; metal whose oxides are not reducible by aluminum with negative elements, the aflinity of one of which for aluminum is less than that of oxygen. 3. A bath for use in the electrolytic production of aluminum comprising a mixture of compounds of aluminum and negative elements of lessyafiinity for aluminum than oxygen in combination with positive eleoxides are not reducible by aluminum.

4; The process of separating aluminum electrolytically which com rises introducing aluminum oxide into a ath, forming an oxide not reducible by aluminum and sepafating the aluminum in combination with a negative element whose afiinity for aluminum is less than that of oxygen.

The process of separating aluminum electrolytically which comprises introducing aluminum oxide-into a bath, forming an oxide not reducible by aluminum and separating the aluminum iii-combination With a negative element whose aflinity for aluminu m is less than that of oxygen, said bath belng substantially free of sodium and potassium.

6. Theprocess of electrolytically separat ing aluminum which comprises simultaneously introducing aluminum oxide and a compound of a more electro-positive element and a negative element of less affinity for aluminumthan oxygen into a bath saturated with the oxygen ion, whereby the oxide of the more electro-positivc element will crystallize out maintaining the composition of the solvent bath-constant.

In test iwmony whereof I afiix my signature.

v JOHN B. RAILSBAGK. 

